CN101161377A - Methods for surface modification of non-dispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method - Google Patents
Methods for surface modification of non-dispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method Download PDFInfo
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- CN101161377A CN101161377A CNA2007101513480A CN200710151348A CN101161377A CN 101161377 A CN101161377 A CN 101161377A CN A2007101513480 A CNA2007101513480 A CN A2007101513480A CN 200710151348 A CN200710151348 A CN 200710151348A CN 101161377 A CN101161377 A CN 101161377A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Abstract
The present invention provides a method for surface modification of non-dispersible metal nanoparticles and the metal nanoparticles for inkjet printing thus modified, in particular, a method for surface modification of non-dispersible metal nanoparticles comprising, mixing metal nanoparticles having an amorphous carbon layer on the surface and an alcohol or thiol solvent, mixing a capping molecule having a carboxylic head group in the mixed solution, and (c) separating the metal nanoparticles from the mixed solution and the metal nanoparticles for inkjet printing thus modified. According to the present invention, the present invention ensures mass production, by converting non-dispersible metal nanoparticles, produced in large quantities, to nanoparticles for inkjet printing.
Description
The cross reference of related application
The application requires the priority of the korean patent application submitted to Korea S Department of Intellectual Property on October 11st, 2006 10-2006-0098805 number, and its full content is hereby expressly incorporated by reference.
Technical field
The present invention relates to a kind of method of surface modification of non-dispersible metal nanoparticles and metal nanoparticle that is used for ink jet printing of modification thus of being used for, especially, relate to a kind of method that is used for the surface modification of non-dispersible metal nanoparticles of paste (paste), provide dispersed and the metal nanoparticle of modification thus with the chemical modification by the surface, wherein the metal nanoparticle of this surface modification is applicable to ink jet printing.
Background technology
Along with the realization of the application of nano particle, prepare in every way and the extensive work that improves nanostructured sharply increases.Because the catalytic performance of their excellences is so furtherd investigate nano particle (the main field of nano science).Recently, repeatedly attempt they are applied to print electronic devices.Using the reason of such nano particle in print electronic devices is in order further to reduce the width of employed wiring in electronic goods.Use paste method plating or applying under the situation of existing reguline metal particle, be difficult to form thin wiring.Therefore, the metal nanoparticle with electric conductivity has been used to realize ultra-fine wiring.
Based on various application facet, there is a large amount of nano particles that is used for paste and ink jet printing.Be whether there is the capping molecule at nano particle that is used for paste and the maximum difference that is used between the nano particle of ink jet printing.The nano particle that is used for paste is used to serigraphy.Because the solvent of paste has high viscosity and dispersant is easy to other interpolation, so just do not need the capping molecule.On the other hand, the nano particle that is used for ink jet printing adds the capping molecule so that dispersion stabilization to be provided with regard to needs, this is because when when nano particle adds other dispersant, influence the surface tension and the viscosity of nano particle, this has adverse effect and can reduce electric conductivity when they further is applied to conducting wiring jetting stability.
Therefore, even the existing nano particle that is used for paste can be used in the cheap large-scale production that utilizes plasma method, but also have problems in its application that is used for aspect the ink jet printing.
Summary of the invention
In order to address the above problem, one aspect of the present invention provides a kind of method that is used for surface modification of non-dispersible metal nanoparticles, it can obtain dispersiveness, so that will be used for the non-dispersible metal nanoparticles nano particle that acts on ink jet printing of paste by chemical surface modification.
The other aspect of the present invention provides the modified nanoparticles that is used for ink jet printing of surface modification thus.
According to following description (comprising accompanying drawing and claim), other aspects and advantages of the present invention will become obviously and be easier to and understand, and perhaps can know by implementing the present invention.
In order to realize technical theme, one aspect of the present invention can provide a kind of method that is used for surface modification of non-dispersible metal nanoparticles, comprising: will have metal nanoparticle and the alcohol or the mercaptan solvent of amorphous carbon layer on the particle surface; The capping molecule (capping molecule) that will have carboxyl head base (headgroup, head group) is sneaked in this mixed solution; And from mixed solution the separating metal nano particle.Metal nanoparticle with amorphous carbon layer can be prepared by the plasma synthetic method.
According to a specific embodiment of the present invention, with respect to the metal nanoparticle of 100 weight portions, alcohol or mercaptan solvent are with 100～5, and 000 weight portion adds.
According to a specific embodiment of the present invention, metal nanoparticle can be finished by back flow reaction with mixing of described solvent.
According to a specific embodiment of the present invention, further comprise: after hybrid metal nano particle and described solvent, toluene added in the mixed solution and with the identical or higher temperature of the boiling temperature of employed alcohol or mercaptan solvent under the described mixed solution of heating.
Wherein, with respect to the metal nanoparticle of 100 weight portions, toluene is with 500～5, and 000 weight portion adds.
According to a specific embodiment of the present invention, in the mixed process of metal nanoparticle and described solvent, may further include and add at least a acid that is selected from the group of forming by hydrochloric acid, sulfuric acid and nitric acid.
Wherein, the concentration of described acid is 0.0001～1M, and with respect to the metal nanoparticle of 1g, and the ml that described acid can 0.1～10 is than adding.
In addition, when adding described acid, the reaction time is 1～30 minute.
According to a specific embodiment of the present invention, utilize capping molecule with hydrophilic tail group, can carry out surface modification to non-dispersible nanoparticles, make this nano particle to be dispersed in the water-miscible organic solvent.
According to a specific embodiment of the present invention, utilize capping molecule with hydrophobic tail base, can carry out surface modification to non-dispersible nanoparticles, make this nano particle to be dispersed in the water-insoluble organic solvents.
According to a specific embodiment of the present invention, with respect to the metal nanoparticle of 100 weight portions, the capping molecule is with 10～3, and 000 weight portion adds.
According to a specific embodiment of the present invention, the mixing of capping molecule can be finished by back flow reaction.Wherein, the hybrid reaction time of capping molecule is 1～10 hour.
The present invention further provides a kind of method of surface modification of non-dispersible metal nanoparticles, this method comprises with the capping molecule with the head base that contains the π key handles the metal nanoparticle that its surface has amorphous carbon layer.
According to a specific embodiment of the present invention, described processing is implemented by adding the capping molecule with the head base that contains the π key after joining at the metal nanoparticle that will have amorphous carbon layer in the alcoholic solvent and stirring.
According to a specific embodiment of the present invention, this head base that contains the π key can be selected from the group of being made up of thiazolinyl, aryl and heteroaryl.
According to a specific embodiment of the present invention, utilization has the capping molecule of hydrophilic tail group, can carry out surface modification to non-dispersible nanoparticles, make this nano particle can be dispersed in the water-miscible organic solvent, and utilization has the capping molecule of hydrophobic tail base, can carry out surface modification to non-dispersible nanoparticles, make this nano particle to be dispersed in the water-insoluble organic solvents.
Wherein, with respect to the metal nanoparticle of 100 weight portions, the content of capping molecule is 10～3,000 weight portion.
According to a specific embodiment of the present invention, after utilizing the processing of capping molecule, may further include the nano particle and reaction of surface modification with polymer of hydrophilic or hydrophobic functional group.
The present invention further provides the metal nanoparticle that is used for ink jet printing, having comprised:
Metal nanoparticle;
Be coated in the lip-deep amorphous carbon layer of this metal nanoparticle; And
Keyed jointing (combination) is in the capping molecule of this amorphous carbon layer.
According to a specific embodiment of the present invention, the nano particle that is used for ink jet printing can prepare by the surface modification non-dispersible metal nanoparticles.
Description of drawings
Fig. 1 is the schematic diagram that illustrates the general building-up process of the nano particle that utilizes plasma.
Fig. 2 is by utilizing the FE-SEM photo of the synthetic copper nano particles of plasma.
Fig. 3 is the schematic diagram by the synthetic nano particle of plasma method.
Fig. 4 is the mechanism according to the surface modification of a specific embodiment of the present invention.
Fig. 5 is the mechanism according to the surface modification of another specific embodiment of the present invention.
Fig. 6 is the mechanism according to the surface modification of another specific embodiment of the present invention.
The specific embodiment
Hereinafter, according to the present invention, detailed description is used for the method for surface modification of non-dispersible metal nanoparticles and the metal nanoparticle that is used for ink jet printing of modification thus.
And, before best explain explanation the specific embodiment of the present invention, with the explanation that at first provides the nano particle that is used for paste for preparing by general plasma synthetic method.
Usually, the nano particle that is used for paste that uses in serigraphy is mainly synthetic by the plasma synthetic method.Fig. 1 is the schematic diagram that illustrates the general synthetic method of the nano particle that utilizes plasma.After gas being activated into plasmoid, from the raw material that utilize plasmatorch to spray, can obtain the particle of nano-scale by a large amount of microwave outputs.He Cheng nano particle has amorphous carbon layer in the most external of this nano particle thus, and this is because the organic material of this precursor is carbonized owing to the high temperature of plasma.
Therefore, although can be used for the high viscosity paste by the synthetic nano particle that forms of plasma,, can not be used to ink jet printing, because particle itself is dispersed relatively poor.
Fig. 2 is the FE-SEM photo by the synthetic copper nano particles of plasma.With reference to Fig. 2, nano particle is of a size of 100nm or littler, but each nano particle is coated with amorphous carbon layer in its surface.
Fig. 3 schematic illustration be coated with the nano particle of amorphous carbon layer.In order to make each nano particle can have dispersiveness, the capping molecule is grafted on the amorphous carbon layer that applies on this nano grain surface.
In the present invention, being coated with the non-general nano particle of amorphous carbon layer that disperses is modified to have dispersiveness, so that they can be used for ink jet printing.
Fig. 4 is the simplification mechanism of surface modifying method of the non-dispersive metal nanoparticle of the specific embodiment according to the present invention.
According to a specific embodiment of the present invention, the surface modifying method of non-dispersible metal nanoparticles comprises: will have metal nanoparticle and the alcohol or the mercaptan solvent of amorphous carbon layer on the particle surface; In this mixed solution, mix capping molecule with carboxyl head base; And from this mixed solution the separating metal nano particle.
At high temperature mix with alcohol or mercaptan solvent if having the metal nanoparticle of amorphous carbon layer, then two bond fissions of lip-deep amorphous carbon layer make can to form hydroxyl (OH) or mercapto (functional group SH).Under the situation that adds acid, can form such as carboxyl (COOH), sulfonic group (SO
3H) etc. functional group.Then, when those functional groups when having the capping molecule aggregation of carboxyl head base, according to the type of the afterbody of capping molecule, this nano particle can be by surface modification can be dispersed in water-soluble solvent or the water-insoluble organic solvents.
According to surface modifying method of the present invention, at first comprise and to have metal nanoparticle and the alcohol or the mercaptan solvent of amorphous carbon layer on the surface.
Metal nanoparticle with amorphous carbon layer can be the metal nanoparticle by above-mentioned general plasma synthetic method preparation.
With respect to the metal nanoparticle of 100 weight portions, alcohol or mercaptan solvent mix with about 100～about 5,000 weight portions.Therefore if the content of this solvent is lower than 100 weight portions, then nano particle can be assembled and the formation of the functional group of activation may be not exclusively.If the content of this solvent surpasses 5,000 weight portions, then not preferred, because untapped excessive solvent still keeps in the reaction.
According to a specific embodiment of the present invention, metal nanoparticle was finished with mixing by back flow reaction of described solvent.Can under the temperature of the boiling temperature that is lower than described alcohol or mercaptan solvent, metal nanoparticle be mixed into stirring simultaneously in the solvent, more preferably, mix by backflow.Backflow can stably remain on the temperature at solvent boiling point temperature place, most preferably, stirs simultaneously by refluxing.
According to a specific embodiment of the present invention, only with alcohol or mercaptan solvent, add in the absence of any acid such as nitric acid etc., in order to form functional group such as hydroxyl, mercapto etc. better, toluene can be joined in the mixed solution.When adding toluene, this mixture of heating forms functional group and removes excessive solvent being easy to owing to intense reaction under the temperature of the boiling point that is higher than alcohol or mercaptan solvent.
Wherein, with respect to the metal nanoparticle of 100 weight portions, toluene adds with about 500～about 5,000 weight portions.If content of toluene is lower than 500 weight portions, then the formation of Huo Hua functional group can be incomplete owing to the gathering of metal nanoparticle.
If content of toluene surpasses 5,000 weight portions, then because this solvent of excessive use and uneconomical.
After the two keys by the fracture amorphous carbon layer formed hydroxyl, the capping molecule that will have carboxyl head base joined in the mixed solution.
The carboxyl of capping molecule and the hydroxyl polymeric of amorphous carbon layer and bonding tightly.Metal nanoparticle can be dispersed in water-miscible organic solvent or the water-insoluble organic solvents, and this depends on the type of the afterbody of capping molecule.If the afterbody of capping molecule is a hydrophilic radical, then non-dispersible nanoparticles can be the surface-modified nano particles that can be dispersed in the water-miscible organic solvent.On the other hand, if this afterbody is a hydrophobic grouping, then non-dispersible nanoparticles can be the surface-modified nano particles that can be dispersed in the water-insoluble organic solvents.
According to a specific embodiment of the present invention, with respect to the metal nanoparticle of 100 weight portions, the capping molecule is with 10～3, and 000 weight portion adds.If the content of capping molecule is lower than 10 weight portions, then not preferred, because capping molecule such as alkyl acid, amino acid etc. can not cover all nano grain surfaces.If the content of capping molecule surpasses 3,000 weight portions, then because excessive use and uneconomical.
Finish with mixing of capping molecule, and the reaction time is 1～10 hour by refluxing.If the reaction time is less than 1 hour, then this finishes before being reflected at the complete bonding of capping molecule.If the reaction time surpasses 10 hours, then not preferred, because this does not have more multiaction to reaction yield.
According to a specific embodiment of the present invention, in the process of hybrid metal nano particle, can further add at least a acid that is selected from the group of forming by hydrochloric acid, sulfuric acid and nitric acid.Fig. 5 shows under the situation that adds acid, a kind of simplification mechanism of surface modification.
According to Fig. 5, when adding acid in the presence of such as the solvent of alcohol etc., two keys of the amorphous carbon layer of metal nanoparticle can rupture and be substituted by functional group such as carboxyl (COOH), sulfonic group (SO
3H) etc.Then, this functional group and carboxyl generation polymerization.
Wherein, the concentration of acid is about 0.0001～about 1M, and with respect to the metal nanoparticle of 1g, this acid with about ml of 0.1～about 10 than adding.Concentration as tartaric acid is lower than 0.0001M or sour to be lower than 0.1ml than adding, and then amorphous carbon layer can not be substituted by functional group such as carboxyl fully.Concentration as tartaric acid surpasses 1M or sour to add greater than the 10ml ratio, then is not preferred, because metal nanoparticle will be destroyed.
In addition, when adding acid, the reaction time is 1～30 minute.If the reaction time is less than 1 minute, then amorphous carbon layer can not be substituted by functional group such as carboxyl fully.If the reaction time surpasses 30 minutes, then metal nanoparticle will be destroyed.
According to a further aspect in the invention, surface modifying method is to finish by handling the metal nanoparticle that has amorphous carbon layer on the particle surface with the capping molecule with π key head base.
Fig. 6 shows the simplification mechanism of above-mentioned surface modifying method.
According to Fig. 6, surface modifying method provides dispersed by the π key that utilizes the amorphous carbon layer on the particle surface for non-dispersible metal nanoparticles, just directly handle, and do not introduce functional group such as hydroxyl, carboxyl etc. with capping molecule with π key head base such as thiazolinyl, aryl and heterocycloalkenyl etc.
According to a specific embodiment of the present invention, such processing is to have the capping molecule that the metal nanoparticle of amorphous carbon layer and alcoholic solvent and adding have a head base that contains the π key by mixing to implement.This head that contains the π key is selected from the group of being made up of thiazolinyl, aryl and heterocycloalkenyl.If use capping molecule with hydrophilic tail group, then can carry out surface modification to non-dispersible nanoparticles, make this nano particle to be dispersed in the water-miscible organic solvent.On the other hand,, then can carry out surface modification, make this nano particle to be dispersed in the water-insoluble organic solvents non-dispersible nanoparticles if use capping molecule with hydrophobic tail base.
Wherein, with respect to the metal nanoparticle of 100 weight portions, the content of capping molecule is about 10～about 3,000 weight portions.Reason as mentioned above.
According to a specific embodiment of the present invention,, use the metal nanoparticle of capping molecular surface modification further to react with polymer with hydrophilic or hydrophobic functional group in order to increase dispersiveness for organic solvent.
According to surface modifying method of the present invention, making can be by utilizing the nano particle (it is to be difficult to large-scale production) that is used for ink jet printing with the mass-produced existing non-dispersible nanoparticles of ton scale (intone scale) with large-scale production.And, owing to be cheap, so the price of the ink-jet (inkjet ink) for preparing by this nano grain surface modification can effectively reduce by the synthetic non-dispersible nanoparticles that waits of plasma.
Another aspect of the present invention provides the nano particle that is used for ink jet printing, comprising: metal nanoparticle; The amorphous carbon layer that on this metal nanoparticle surface, applies; And the capping molecule that is bonded to this amorphous carbon layer.
The nano particle that is used for ink jet printing can prepare by surface modification non-dispersible metal nanoparticles as mentioned above, the nanometer ink that such surface-modified nano particles can be used for ink jet printing in preparation provides dispersiveness in organic solvent because be bonded in capping molecule on the amorphous carbon layer of great use.
Hereinafter, explain though utilize specific embodiment to provide in more detail, the present invention is not limited to the embodiment of following statement.
Embodiment 1
The nano particle that the amorphous carbon of 1g is applied joins and stirs simultaneously in the ethanol of 10ml and reflux.Afterwards, the toluene that adds 30g.With temperature be elevated to be higher than alcohol boiling point to remove this alcohol.Add the oleic acid of 10g and this solution was under refluxad reacted 4 hours.Afterwards, by filter to isolate nano particle and with the nano particle of this separation of toluene wash of 30ml above 3 times.These nano particles are dry in 50 ℃ vacuum drying oven, to generate the nano particle that can be dispersed in the organic solvent.
Embodiment 2
The nano particle that the amorphous carbon of 1g is applied joins in the ethanol of 10ml and stirs simultaneously.After the 0.01M nitric acid that adds 0.1ml, this reaction solution was under refluxad reacted 10 minutes.Afterwards, by filtering and centrifugally coming separating nano-particles and drying in vacuum drying oven.This nano particle of 1g is dissolved in the ethanol of 10ml.Afterwards, join 1-hydroxyl-2-naphthoic acid of 10g in the reaction solution and this reaction solution was under refluxad reacted 4 hours.Afterwards, also wash the nano particle of this separation above 3 times by the isolated by filtration nano particle with the ethanol of 30ml.These nano particles are dry in 50 ℃ vacuum drying oven, to generate the nano particle that can be dispersed in the water-based solvent.
Embodiment 3
The nano particle that the amorphous carbon of 1g is applied joins in the ethanol of 10ml and stirs simultaneously.After the 0.01M sulfuric acid that adds 0.1ml, this reaction solution was under refluxad reacted 10 minutes.Afterwards, by filtering and centrifugally coming separating nano-particles and drying in vacuum drying oven.Afterwards, make the SOCl of this nano particle and 20ml
2Reacted 1 hour down at 65 ℃, with lip-deep carboxyl substituted to be-the COCl group.The nano particle of 1g surface modification is dissolved in the ethanol of 10ml.Afterwards, add 1 of 10g, 2-two-(10,12-two oleatridecadiene acyl groups)-sn-glycerol-3-phosphate monoethanolamine also under refluxad reacted this reaction solution 4 hours.Afterwards, also wash the nano particle of this separation above 3 times by the isolated by filtration nano particle with the ethanol of 30ml.These nano particles are dry in 50 ℃ vacuum drying oven, to generate the nano particle that can be dispersed in the water-based solvent.
Embodiment 4
The nano particle that the amorphous carbon of 1g is applied joins in the ethanol of 10ml and stirs simultaneously.At the 1-pyrene propyl group amine hydrochlorate (PyrNH that adds 10g
3) afterwards, stirred this reaction solution 3 hours.Afterwards, by filter and centrifugal come separating nano-particles and in vacuum drying oven drying, have PyrNH on the surface to provide
3Nano particle.Join the polymer (polystyrene sodium sulfate salt) of 10g in this reaction solution and reacted 5 hours.Afterwards, also wash the nano particle of this separation above 3 times by the isolated by filtration nano particle with the ethanol of 30ml.These nano particles are dry in 50 ℃ vacuum drying oven, to generate the nano particle that can be dispersed in the water-based solvent.
The present invention is not limited to the foregoing description, and also can be apparent, and under the situation that does not deviate from principle of the present invention and spirit, those skilled in the art can more change.
Claims (24)
1. method that is used for surface modification of non-dispersible metal nanoparticles, described method comprises:
Metal nanoparticle and the alcohol or the mercaptan solvent of amorphous carbon layer will be had on the described particle surface;
In described mixed solution, mix capping molecule with carboxyl head base; And from described mixed solution, separate described metal nanoparticle.
2. method according to claim 1, wherein, described metal nanoparticle with amorphous carbon layer prepares by the plasma synthetic method.
3. method according to claim 1, wherein, with respect to the described metal nanoparticle of 100 weight portions, described alcohol or mercaptan solvent mix with about 100～about 5,000 weight portions.
4. method according to claim 1, wherein, described nano particle with finish alcohol or mixing of mercaptan solvent by back flow reaction.
5. method according to claim 1 further comprises:
After hybrid metal nano particle and alcohol or mercaptan solvent, toluene is joined in the described mixed solution; And
The described mixture of heating under the boiling temperature of described alcohol or mercaptan solvent or higher temperature.
6. method according to claim 5, wherein, with respect to the described metal nanoparticle of 100 weight portions, described toluene adds with about 500～about 5,000 weight portions.
7. method according to claim 1, wherein, described metal nanoparticle adds at least a acid that is selected from the group of being made up of hydrochloric acid, sulfuric acid and nitric acid with further comprising mixing of alcohol or mercaptan solvent.
8. method according to claim 7, wherein, the concentration of described acid is about 0.0001～about 1M, and with respect to the described metal nanoparticle of 1g, described acid with about ml of 0.1～about 10 than adding.
9. method according to claim 7, wherein, if add described acid, the hybrid reaction time of then described metal nanoparticle and alcohol or mercaptan solvent is about 1～about 30 minutes.
10. method according to claim 1, wherein, described capping molecule comprises hydrophily tail base and described non-dispersible nanoparticles is modified as the nano particle that can be dispersed in the water-miscible organic solvent.
11. method according to claim 1, wherein, described capping molecule comprises hydrophobicity tail base and described non-dispersible nanoparticles is modified as the nano particle that can be dispersed in the water-insoluble organic solvents.
12. method according to claim 1, wherein, with respect to the described metal nanoparticle of 100 weight portions, described capping molecule adds with about 10～about 3,000 weight portions.
13. method according to claim 1 wherein, and is finished described the mixing by back flow reaction of described capping molecule.
14. method according to claim 1, wherein, with described reaction time of mixing of described capping molecule be 1～10 hour.
15. a method that is used for surface modification of non-dispersible metal nanoparticles comprises with the capping molecule with the head base that contains the π key and handles the metal nanoparticle that has amorphous carbon layer on the described particle surface.
16. method according to claim 15, wherein, described processing is to join to stir simultaneously in the alcoholic solvent and add the described capping molecule with the head base that contains the π key by the described metal nanoparticle that will have amorphous carbon layer to stir simultaneously and finish.
17. method according to claim 15, wherein, the head base of the described π of containing key is selected from the group of being made up of aryl, thiazolinyl and heteroaryl.
18. method according to claim 15, wherein, described capping molecule comprises hydrophily tail base and described non-dispersible nanoparticles is modified as the nano particle that can be dispersed in the water-miscible organic solvent.
19. method according to claim 15, wherein, described capping molecule comprises hydrophobicity tail base and described non-dispersible nanoparticles is modified as the nano particle that can be dispersed in the water-insoluble organic solvents.
20. method according to claim 15, wherein, with respect to the described metal nanoparticle of 100 weight portions, the content of described capping molecule is about 10～about 3,000 weight portions.
21. method according to claim 15 further is included in after the described processing with described capping molecule, makes the nano particle of described surface modification and the polymer reaction with hydrophilic or hydrophobic functional group.
22. be used for the metal nanoparticle of ink jet printing, comprise:
Metal nanoparticle;
Be coated in the lip-deep amorphous carbon layer of described metal nanoparticle; And the capping molecule that is bonded in described amorphous carbon layer.
23. metal nanoparticle according to claim 22, wherein, the described metal nanoparticle that is used for ink jet printing is the method preparation by the surface modification of the described non-dispersible metal nanoparticles of claim 1.
24. an electrical-conductive nanometer ink comprises the metal nanoparticle that is used for ink jet printing according to claim 22.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2006-0098805 | 2006-10-11 | ||
| KR20060098805A KR100830871B1 (en) | 2006-10-11 | 2006-10-11 | Method for surface modification of nondispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method |
| KR1020060098805 | 2006-10-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101161377A true CN101161377A (en) | 2008-04-16 |
| CN101161377B CN101161377B (en) | 2010-06-02 |
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ID=39296405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101513480A Expired - Fee Related CN101161377B (en) | 2006-10-11 | 2007-09-25 | Methods for surface modification of non-dispersible metal nanoparticles and modified metal nanoparticles for inkjet by the same method |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US8173210B2 (en) |
| JP (1) | JP2008095197A (en) |
| KR (1) | KR100830871B1 (en) |
| CN (1) | CN101161377B (en) |
Cited By (6)
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- 2006-10-11 KR KR20060098805A patent/KR100830871B1/en not_active IP Right Cessation
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- 2007-09-25 CN CN2007101513480A patent/CN101161377B/en not_active Expired - Fee Related
- 2007-10-10 JP JP2007264546A patent/JP2008095197A/en active Pending
- 2007-10-10 US US11/907,173 patent/US8173210B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102223972A (en) * | 2008-10-24 | 2011-10-19 | 普里梅精密材料有限公司 | Group iva small particle compositions and related methods |
| CN101775631B (en) * | 2009-12-29 | 2012-12-19 | 昆明理工大学 | Method for preparing lead dioxide based composite plating layer containing nano rare earth and nano zirconium dioxide |
| CN102554217A (en) * | 2012-02-24 | 2012-07-11 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN102554217B (en) * | 2012-02-24 | 2014-12-17 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN105980491A (en) * | 2014-01-13 | 2016-09-28 | 伊斯曼柯达公司 | Coated nano-particle catalytically active composite inks |
| CN103785826A (en) * | 2014-02-19 | 2014-05-14 | 南京林业大学 | Method for preparing modified nanometer nickel powder |
| CN103785826B (en) * | 2014-02-19 | 2016-03-30 | 南京林业大学 | A kind of preparation method of modified Nano nickel powder |
| CN104130629A (en) * | 2014-07-30 | 2014-11-05 | 深圳市宇顺电子股份有限公司 | Electric-conduction ink and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US8173210B2 (en) | 2012-05-08 |
| JP2008095197A (en) | 2008-04-24 |
| CN101161377B (en) | 2010-06-02 |
| US20080090082A1 (en) | 2008-04-17 |
| KR20080032814A (en) | 2008-04-16 |
| KR100830871B1 (en) | 2008-05-21 |
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